FCC Catalyst Compositions Containing Boron Oxide

ABSTRACT

Described are fluid catalytic cracking (FCC) compositions, methods of manufacture and use. FCC catalyst compositions comprise particles containing a non-zeolitic component and one or more boron oxide components. In embodiments, the FCC catalyst composition contains a zeolite component and optionally a rare earth component and a transition alumina. FCC catalytic compositions may comprise a first particle type containing one or more boron oxide components and a first matrix component mixed with a second particle type containing a second matrix component, and a zeolite. The FCC catalyst compositions can be used to crack hydrocarbon feeds, particularly resid feeds containing high V and Ni, resulting in lower hydrogen and coke yields.

TECHNICAL FIELD

The present invention relates to a fluid catalytic cracking catalyst andto a hydrocarbon catalytic cracking process using the catalyst. Moreparticularly, the invention relates to a fluid catalytic crackingcatalyst composition comprising one or more boron oxide components forimproved catalytic performance in the presence of contaminant metals.

BACKGROUND

Catalytic cracking is a petroleum refining process that is appliedcommercially on a very large scale. Catalytic cracking, and particularlyfluid catalytic cracking (FCC), is routinely used to convert heavyhydrocarbon feedstocks to lighter products, such as gasoline anddistillate range fractions. In FCC processes, a hydrocarbon feedstock isinjected into the riser section of a FCC unit, where the feedstock iscracked into lighter, more valuable products upon contacting hotcatalyst circulated to the riser-reactor from a catalyst regenerator.

It has been recognized that for a fluid catalytic cracking catalyst tobe commercially successful, it must have commercially acceptableactivity, selectivity, and stability characteristics. It must besufficiently active to give economically attractive yields, have goodselectivity towards producing products that are desired and notproducing products that are undesired, and it must be sufficientlyhydrothermally stable and attrition resistant to have a commerciallyuseful life.

Exccessive coke and hydrogen is undesirable in commercial catalyticcracking processes. Even small increases in the yields of these productsrelative to the yield of gasoline can cause significant practicalproblems. For example, increases in the amount of coke produced cancause undesirable increases in the heat that is generated by burning offthe coke during the highly exothermic regeneration of the catalyst.Conversely, insufficient coke production can also distort the heatbalance of the cracking process. In addition, in commercial refineries,expensive compressors are used to handle high volume gases, such ashydrogen. Increases in the volume of hydrogen produced, therefore, canadd substantially to the capital expense of the refinery.

Improvements in cracking activity and gasoline selectivity of crackingcatalysts do not necessarily go hand in hand. Thus, a cracking catalystcan have outstandingly high cracking activity, but if the activityresults in a high level of conversion to coke and/or gas at the expenseof gasoline the catalyst will have limited utility. Catalytic crackingin current FCC catalysts is attributable to both the zeolite andnon-zeolite (e.g. matrix) components. Zeolite cracking tends to begasoline selective, while matrix cracking tends to be less gasolineselective.

In recent years, the oil refining industry has shifted to processing alarger quantity of residual (resid) and resid-containing feeds due tochanges in the price structure and availability of crude oil. Manyrefiners have been processing at least a portion of residual oil intheir units and several now run a full residual oil cracking program.Processing resid feeds can drastically alter yields of valuable productsin a negative direction relative to a light feed. Aside from operationaloptimizations, the catalyst has a large impact on product distribution.Several factors are important to resid catalyst design. It is highlyfavorable if the catalyst can minimize coke and hydrogen formation, havehigh stability, and minimize deleterious contaminant selectivity due tometal contaminants in resid feedstocks.

Resid feeds typically contain contaminant metals including Ni, V, Fe,Na, Ca, and others. Resid FCC for converting heavy resid feeds with highNi and V contaminants constitutes the fastest growing FCC segmentglobally. Both Ni and V catalyze unwanted dehydrogenation reactions, butNi is an especially active dehydrogenation catalyst. Ni significantlyincreases H₂ and coke yields. In addition to taking part in unwanteddehydrogenation reactions, V comes with other major concerns as it ishighly mobile under FCC conditions and its interaction with the zeolitedestroys its framework structure, which manifests itself as increased H₂and coke yields, as well as lower zeolite surface area retention. Evensmall amounts (e.g., 1-5 ppm) of contaminant metals in the feedcumulatively deposited on the catalyst can result in high H₂ and cokeyields during FCC operation, if the catalyst does not feature anoptimized metals passivation system, which is a major concern for therefining industry.

Since the 1960s, most commercial fluid catalytic cracking catalysts havecontained zeolites as an active component. Such catalysts have taken theform of small particles, referred to as microspheres, containing both anactive zeolite component and a non-zeolite component in the form of ahigh alumina, silica-alumina (aluminosilicate) matrix. The activezeolitic component is incorporated into the microspheres of the catalystby one of two general techniques. In one technique, the zeoliticcomponent is crystallized and then incorporated into microspheres in aseparate step. In the second technique, the in situ technique,microspheres are first formed and the zeolitic component is thencrystallized in the microspheres themselves to provide microspherescontaining both zeolitic and non-zeolitic components. For many years asignificant proportion of commercial FCC catalysts used throughout theworld have been made by in situ synthesis from precursor microspherescontaining kaolin that had been calcined at different severities priorto formation into microspheres by spray drying. U.S. Pat. No. 4,493,902(“the '902 patent”), incorporated herein by reference in its entirety,discloses the manufacture of fluid cracking catalysts comprisingattrition-resistant microspheres containing Y zeolite with faujisitestructure, formed by crystallizing sodium Y zeolite in porousmicrospheres composed of metakaolin and spinel. The microspheres in the'902 patent contain more than about 40%, for example 50-70% by weight Yzeolite. Such catalysts can be made by crystallizing more than about 40%sodium Y zeolite in porous microspheres composed of a mixture of two ormore different phases of chemically reactive calcined clay, namely,metakaolin (kaolin calcined to undergo a strong endothermic reactionassociated with dehydroxylation) and kaolin clay calcined underconditions more severe than those used to convert kaolin to metakaolin,i.e., kaolin clay calcined to undergo the characteristic kaolinexothermic reaction, sometimes referred to as the spinel form ofcalcined kaolin. This characteristic kaolin exothermic reaction issometimes referred to as kaolin calcined through its “characteristicexotherm.” The microspheres containing the two forms of calcined kaolinclay are immersed in an alkaline sodium silicate solution, which isheated, until the desired amount of Y zeolite with faujasite structureis crystallized in the microspheres.

Fluid cracking catalysts which contain silica-alumina or aluminamatrices are termed catalysts with “active matrix.” Catalysts of thistype can be compared with those containing untreated clay or a largequantity of silica, which are termed “inactive matrix” catalysts. Inrelation to catalytic cracking, despite the apparent disadvantage inselectivity, the inclusion of aluminas or silica-alumina has beenbeneficial in certain circumstances. For instance when processing ahydrotreated/demetallated vacuum gas oil (hydrotreated VGO) the penaltyin non-selective cracking is offset by the benefit of cracking or“upgrading” the larger feed molecules which are initially too large tofit within the rigorous confines of the zeolite pores. Once “precracked”on the alumina or silica-alumina surface, the smaller molecules may thenbe selectively cracked further to gasoline material over the zeoliteportion of the catalyst. While one would expect that this precrackingscenario might be advantageous for resid feeds, they are, unfortunately,characterized as being heavily contaminated with metals such as nickeland vanadium and, to a lesser extent, iron. When a metal such as nickeldeposits on a high surface area alumina such as those found in typicalFCC catalysts, it is dispersed and participates as highly active centersfor the catalytic reactions which result in the formation of contaminantcoke (contaminant coke refers to the coke produced discretely fromreactions catalyzed by contaminant metals) and hydrogen. This additionalcoke exceeds that which is acceptable by refiners. Loss of activity orselectivity of the catalyst may also occur if the metal contaminants(e.g. Ni, V) from the hydrocarbon feedstock deposit onto the catalyst.These metal contaminants are not removed by standard regeneration(burning) and contribute to high levels of hydrogen, dry gas and coke,and reduce significantly the amount of gasoline that can be made.

U.S. Pat. No. 4,192,770 describes a process of restoring selectivity ofcracking catalysts which are contaminated with metals during catalyticcracking operations. The catalysts are restored by adding boron toeither the fresh make-up catalyst or to the catalyst during operations.One problem with this approach is that boron is directly placed on thecatalyst, which may negatively impact the catalyst material. Inaddition, such an approach addresses the problem after it has occurred,by treating the catalyst after it has been contaminated. U.S. Pat. No.4,295,955 utilizes a similar approach by restoring catalyst that hasbeen contaminated with metals. U.S. Pat. No. 4,295,955 also shows in theexamples that fresh catalyst can be treated with boron to attenuateresidual metals on the fresh catalyst that contribute to the undesirableyield of hydrogen. U.S. Pat. Nos. 5,5151,394 and 5,300,215 disclosecatalyst compositions comprising molecular sieve materials and a boronphosphate matrix. The Examples state that the addition of boronphosphate to the matrix does not change the physical properties orattrition resistance, but the addition of boron phosphate producedgasoline with higher octane in a cracking process.

While the aforementioned patents show the utility of boron compounds fortreating contaminated catalysts and attenuating residual metals oncatalyst materials, it would be desirable to provide materials thatallow the addition of boron to FCC processes and units under dynamic andvarying conditions. It also would be desirable to provide FCC processesand FCC catalyst compositions that can reduce coke and hydrogen yieldsfor a variety of FCC unit conditions and hydrocarbon feeds, for example,feeds containing high levels of transition metals, such as resid feeds.

SUMMARY

One aspect of the invention is directed to a fluid catalytic cracking(FCC) catalyst composition for cracking hydrocarbons. Variousembodiments are listed below. It will be understood that the embodimentslisted below may be combined not only as listed below, but in othersuitable combinations in accordance with the scope of the invention.

In embodiment one, the catalyst composition comprises: FCC compatibleinorganic particles containing one or more boron oxide components andcracking particles, the FCC catalyst composition effective to reducecoke and hydrogen yields during cracking of metal-containing FCC feeds.

Embodiment two is directed to a modification of catalyst compositionembodiment one, wherein the one or more boron oxide components arepresent in an amount in the range of 0.005% to 8% by weight of thecomposition.

Embodiment three is directed to a modification of catalyst compositionembodiment one or two, wherein the cracking particles comprise 20% to95% by weight of a zeolite component.

Embodiment four is directed to a modification of any of catalystcomposition embodiments one through three, wherein the FCC compatibleinorganic particle comprises a non-zeolitic component.

Embodiment five is directed to a modification of any of catalystcomposition embodiments one through four, wherein the non-zeoliticcomponent is selected from the group consisting of kaolinite,halloysite, montmorillonite, bentonite, attapulgite, kaolin, amorphouskaolin, metakaolin, mullite, spinel, hydrous kaolin, clay, gibbsite(alumina trihydrate), boehmite, titania, alumina, silica,silica-alumina, silica-magnesia, magnesia and sepiolite.

Embodiment six is directed to a modification of any of catalystcomposition embodiments one through five, wherein the cracking particlecontains oxide is selected from the group consisting of yttria, ceria,lanthana, praseodymia, neodymia, and combinations thereof.

Embodiment seven is directed to a modification of any of catalystcomposition embodiments one through six, wherein the rare earthcomponent is lanthana, and the lanthana is present in a range of 0.5 wt.% to about 5.0 wt. % on an oxide basis based on the weight of the FCCcatalyst composition.

Embodiment eight of the invention is directed to a modification of anyof catalyst composition embodiments one through seven, the crackingparticle further comprising a transition alumina component present in arange of 1 wt. % to 35 wt. %.

Embodiment nine is directed to a modification of any of catalystcomposition embodiments one through eight, wherein the zeolite isintergrown with the non-zeolitic component.

Embodiment ten is directed to a modification of any of catalystcomposition embodiments one through nine, wherein the zeolite componentis mixed with the non-zeolitic component.

Embodiment eleven is directed to a modification of any of catalystcomposition embodiments one through ten, wherein the one or more boronoxide components are on the cracking particles.

Another aspect of the invention pertains to an FCC catalyst compositionfor cracking hydrocarbons. Therefore, embodiment twelve is directed to acatalyst composition comprising a first particle type comprising one ormore boron oxide components and a first matrix component and a secondparticle type having a composition different from the first particletype, the second particle type comprising a second matrix component and20% to 95% by weight of a zeolite component, wherein the first particletype and second particle type are mixed together.

Embodiment thirteen is directed to a modification of catalystcomposition embodiment twelve, wherein the first and second matrixcomponents comprise a non-zeolitic material.

Embodiment fourteen is directed to a modification of any of catalystcomposition embodiment twelve or thirteen, wherein the one or more boronoxide components are on second particle type.

Embodiment fifteen is directed to a modification of any of methodembodiments twelve through fourteen, wherein the non-zeolitic materialis selected from the group consisting of kaolinite, halloysite,montmorillonite, bentonite, attapulgite, kaolin, amorphous kaolin,metakaolin, mullite, spinel, hydrous kaolin, clay, gibbsite (aluminatrihydrate), boehmite, titania, alumina, silica, silica-alumina,silica-magnesia, magnesia and sepiolite.

Another aspect of the invention pertains to a method of cracking ahydrocarbon feed under fluid catalytic cracking conditions. Therefore,embodiment sixteen is directed to a method comprising contacting thehydrocarbon feed with any of the catalyst composition embodiments onethrough eleven.

Another aspect of the invention pertains to a method of cracking ahydrocarbon feed under fluid catalytic cracking conditions. Therefore,embodiment seventeen is directed to a method comprising contacting thehydrocarbon feed with any of the catalyst composition embodiments twelvethrough fifteen.

Another aspect of the invention pertains to method of manufacturing afluid catalytic cracking catalyst (FCC) composition. Therefore,embodiment eighteen is directed to a method comprising forming particlescontaining a non-zeolitic component and one or more boron oxides.

Embodiment nineteen is directed to a modification of method embodimenteighteen, wherein the one or more boron oxides are impregnated onto theparticles.

Embodiment twenty is directed to a modification of method embodimenteighteen or nineteen, wherein the one or more boron oxides are mixedwith the non-zeolitic component and spray dried to form the particles.

Embodiment twenty-one is directed to a modification of any of methodembodiments eighteen through nineteen, wherein the formed particlesfurther comprise a molecular sieve.

Embodiment twenty-two is directed to a modification of any of methodembodiments eighteen through twenty-one, wherein the one or more boronoxides are loaded on non-zeolitic particles.

Embodiment twenty-three is directed to a modification of any of methodembodiments eighteen through twenty-two, wherein one or more boron oxidecomponents are added to non-zeolitic particles during calcination of theparticles.

Embodiment twenty-four is directed to a modification of any of methodembodiments eighteen through twenty-three, wherein the non-zeoliticmaterial is selected from the group consisting of kaolinite, halloysite,montmorillonite, bentonite, attapulgite, kaolin, amorphous kaolin,metakaolin, mullite, spinel, hydrous kaolin, clay, gibbsite (aluminatrihydrate), boehmite, titania, alumina, silica, silica-alumina,silica-magnesia, magnesia and sepiolite, the particle further comprisinga transition alumina and a zeolite component intergrown in situ with theparticles.

DETAILED DESCRIPTION

Before describing several exemplary embodiments of the invention, it isto be understood that the invention is not limited to the details ofconstruction or process steps set forth in the following description.The invention is capable of other embodiments and of being practiced orbeing carried out in various ways.

Each FCC unit has a unique capacity and hydrocarbon feed, which meansthat a variety of boron-containing catalyst materials containingdifferent amounts of boron are needed. For example, resid feeds havehigher metals content than other types of hydrocarbon feeds, which mayrequire more boron than other hydrocarbon feeds that have lower metalscontent. Furthermore, even in the same FCC unit, the catalyst in theunit degrades over time, and it may be desirable to increase or decreasethe amount of boron in the unit to address the metals content of aparticular process at a particular time. Also, the quality of thehydrocarbon feed can change over time, and some hydrocarbon feeds mayrequire a different boron content to handle the different metalscontent. Further, it would be desirable to provide processes in whichboron is not placed in direct contact with zeolite on the crackingparticles when the boron is applied to the material that is added to theunit. Boron can have a deleterious effect on zeolite, for example,causing dealumination and/or partial loss of crystallinity. It would bedesirable to provide a boron-containing additive that could be used witha variety of FCC catalyst compositions that address metals content undera variety of conditions. In particular, it would be desirable to providea way of providing varied boron content to various FCC feeds byutilizing solid, inert, FCC compatible inorganic particles containingboron, which also avoids direct application of boron materials to thecracking particles.

As used herein, “cracking particle” refers to a particle which containsan active cracking component conventionally present to effect the moreselective hydrocarbon cracking reactions to provide more desiredproducts such as gasoline, propylene and LPG. Normally, the activecracking component to effect the more selective hydrocarbon crackingreactions comprises a molecular sieve such as a zeolite. The activecracking component is combined with a matrix material such as silica oralumina as well as a clay to provide the desired mechanicalcharacteristics such as attrition resistance. It is understood that thematrix material has some cracking activity, but matrix material is lessselective in cracking. As used herein, “FCC compatible inorganicparticle” is a particle that is less selective in providing the morevaluable products such as gasoline, propylene and LPG. Particles may bein the form of microspheres.

As used herein, “mobile,” refers to the ability of boron to move withinand between particle types in the FCC unit.

Thus, the FCC compatible inorganic particles can be present in a rangeof 1% to 40% by weight of the FCC catalyst composition. Thus, there isbetween 60 and 99% by weight of cracking particles by weight of the FCCcatalyst composition. Examples of amounts of FCC compatible inorganicparticles based on the total weight of the FCC catalyst compositioninclude 1,%, 2%, 3%, 4%, 5%, 6,%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%,35% and 40%. Examples of amounts of cracking particles based on thetotal weight of the FCC catalyst composition include 99%, 98%, 97%, 96%,95%, 94%, 93%, 92%, 91%, 90%, 85%, 80%, 75%, 70%, 65% and 60%. In one ormore embodiments, the FCC compatible inorganic particles contain one ormore boron oxides in the range of 0.005% to 20% by weight of the FCCcompatible inorganic particles. When added to the cracking particles,the amount of boron present is in the range of 0.005 and 8% on an oxidebasis based upon the total weight of FCC compatible inorganic particleand cracking particles in the FCC unit.

Embodiments of the present invention provide a FCC catalyst composition,which uses one or more boron oxide components for metal, particularly,nickel passivation. The presence of boron oxide in a fluid catalyticcracking catalyst as a trapping/passivating material results in lowerhydrogen and coke yields when processing heavy hydrocarbons feeds,particularly resid feeds, contaminated with transition metals.Passivating or passivation refers to the ability of the boron componentto reduce or prevent the activity of deleterious metals (such as nickel)from negatively impacting the selectivity of the FCC process. Providedherein are FCC catalysts, methods of making FCC catalysts, and methodsof cracking hydrocarbon feeds.

One aspect of the invention relates to a fluid catalytic cracking (FCC)catalyst composition for cracking hydrocarbons, the FCC catalystcomposition comprising FCC compatible inorganic particles, and one ormore boron oxide components, the FCC catalyst composition effective toreduce coke and hydrogen yields during cracking of hydrocarbons.Lowering hydrogen yields is beneficial in wet gas compressor-limitedprocesses. In one or more embodiments, the FCC compatible inorganicparticles can include one or more of metakaolin, spinel, kaolin andmullite. The FCC catalyst composition is typically in the form ofparticles, more specifically as microspheres, which will be describedfurther below.

The non-zeolitic material may also be referred to as matrix material, asdiscussed further below. In one embodiment of the invention, a FCCcatalyst composition comprises particles consisting essentially ofmatrix material and one or more boron oxides. This composition,consisting essentially of matrix material and one or more boron oxides,provides a first particle type. In one embodiment, this first particletype can be used together with existing FCC catalyst compositions toreduce coke and hydrogen yields during cracking processes. For example,the first particle type may be introduced into an FCC unit with a secondparticle type, the second particle type comprising a non-zeoliticcomponent, a transition alumina component, a zeolite component, and arare earth component.

As an alternative to providing a first particle type and a secondparticle type, one or more boron oxides can be used in a FCC catalystcomposition comprising particles containing a non-zeolitic component, atransition alumina component, a zeolite component, and a rare earthcomponent. In this alternative approach, the boron and the active FCCcatalyst are incorporated into an all-in-one particle. According toembodiments of the present invention, when present in the composition,the zeolite component is present in a range of 20% to 95% by weightbased on the catalyst composition.

Thus, embodiments of the invention provide FCC catalyst compositionscomprising particles comprising a non-zeolitic matrix, and one or moreboron oxide components. Providing two separate particle types allowsboron oxide-containing particles to be added to a FCC catalystcomposition in the unit as needed to passivate feeds having high metalcontents.

Thus, embodiments of the present invention provide FCC catalystcompositions using boron oxide-modified particles, which, according toone or more embodiments, can be made by spray drying a mixture ofmullite, hydrous kaolin, and a suitable binder, for example, a silicatebinder, and then modifying the particles with one or more boron oxidecomponents as described below. In one or more embodiments, the boron canbe added during spray-drying. In embodiments in which the catalystcomposition comprises a single particle type containing boron, theparticles may also include a transition alumina and a zeolite. Thezeolite can be added as separate particles to the composition duringspray drying, or the zeolite can be intergrown in the particlecomposition by the in situ crystallization of the zeolite. The particlesmay further include a rare earth component. Thus, in an embodiment ofthe invention, particles are provided which contain a non-zeoliticcomponent, a zeolite, a transition alumina, a rare earth component, andone or more boron oxide components.

In an alternative embodiment, as noted above, a first microsphere typecomprises a non-zeolitic matrix and one or more boron oxide components,and a second microsphere type comprising a non-zeolitic matrix, atransition alumina, a zeolite, and a rare earth component.

According to one or more embodiments, a catalyst composition is providedwhich exhibits higher performance in which a mobile boron oxide speciesprevents contaminant metals from interfering with catalyst selectivity,and reducing coke and hydrogen yield.

With respect to the terms used in this disclosure, the followingdefinitions are provided.

As used herein, the term “catalyst” or “catalyst composition” or“catalyst material” refers to a material that promotes a reaction.

As used herein, the term “fluid catalytic cracking” or “FCC” refers to aconversion process in petroleum refineries wherein high-boiling,high-molecular weight hydrocarbon fractions of petroleum crude oils areconverted to more valuable gasoline, olefinic gases, and other products.

As used herein, the term “feed” or “feedstock” refers to that portion ofcrude oil that has a high boiling point and a high molecular weight. InFCC processes, a hydrocarbon feedstock is injected into the risersection of a FCC unit, where the feedstock is cracked into lighter, morevaluable products upon contacting hot catalyst circulated to theriser-reactor from a catalyst regenerator.

“Cracking conditions” or “FCC conditions” refers to typical FCC processconditions. Typical FCC processes are conducted at reaction temperaturesof 450° to 650° C. with catalyst regeneration temperatures of 600° to850° C. Hot regenerated catalyst is added to a hydrocarbon feed at thebase of a rise reactor. The fluidization of the solid catalyst particlesmay be promoted with a lift gas. The catalyst vaporizes and superheatsthe feed to the desired cracking temperature. During the upward passageof the catalyst and feed, the feed is cracked, and coke deposits on thecatalyst. The coked catalyst and the cracked products exit the riser andenter a solid-gas separation system, e.g., a series of cyclones, at thetop of the reactor vessel. The cracked products are fractionated into aseries of products, including gas, gasoline, light gas oil, and heavycycle gas oil. Some heavier hydrocarbons may be recycled to the reactor.

As used herein, the term “resid” refers to that portion of crude oilthat has a high boiling point and a high molecular weight and typicallycontains contaminant metals including Ni, V, Fe, Na, Ca, and others. Thecontaminant metals, particularly Ni and V, have detrimental effects oncatalyst activity and performance. In some embodiments, in a resid feedoperation, one of Ni and V metals accumulate on the catalyst, and theFCC catalyst composition is effective to reduce the detrimental effectsof nickel and vanadium during cracking.

As used herein, the term “one or more boron oxide components” refers tothe presence of multiple species of boron oxide. For example, in one ormore embodiments, boron oxide components can include a boron oxide in atrigonal environment (e.g. BO₃) and in a tetrahedral oxygen environment(e.g. BO₄—). Differences in the chemical composition of the boron oxidespecies after reaction with FCC catalysts containing Ni and other metalscan be observed by peak changes in boron nuclear magnetic resonance (¹¹BNMR) analyses. It is believed that boron oxide can interact withtransition metals, such as Ni and V, and inhibit the dehydrogenationactivity of the transition metal by forming a metal-borate (e.g.Ni-borate) complex, which results in a reduction in coke and hydrogenyields during cracking of hydrocarbons. However, because boron oxide ismobile under typical FCC conditions, the trapping mechanism is differentthan that of a transition alumina.

As used herein, “particles” can be in the form of microspheres which canbe obtained by spray drying. As is understood by skilled artisans,microspheres are not necessarily perfectly spherical in shape.

As used herein, the term “non-zeolitic component” refers to thecomponents of a FCC catalyst that are not zeolites or molecular sieves.As used herein, the non-zeolitic component can comprise binder andfiller. The phrase “non-zeolitic component” may be used interchangeablywith the phrase “matrix material.” According to one or more embodiments,the “non-zeolitic component” can be selected from the group consistingof kaolinite, halloysite, montmorillonite, bentonite, attapulgite,kaolin, amorphous kaolin, metakaolin, mullite, spinel, hydrous kaolin,clay, gibbsite (alumina trihydrate), boehmite, titania, alumina, silica,silica-alumina, silica-magnesia, magnesia and sepiolite.

As used herein, the term “molecular sieve” refers to a materialcomprising a framework based on an extensive three-dimensional networkof oxygen ions containing generally tetrahedral type sites. As usedherein, the term “zeolite” refers to a molecular sieve, which is acrystalline aluminosilicate with a framework based on an extensivethree-dimensional network of oxygen ions and have a substantiallyuniform pore distribution.

As used herein, the term “in situ crystallized” refers to the process inwhich a zeolite is grown or intergrown directly on/in a microsphere andis intimately associated with the matrix or non-zeolitic material forexample, as described in U.S. Pat. Nos. 4,493,902 and 6,656,347.“Transition alumina” is defined as any alumina which is intermediatebetween the thermodynamically stable phases of gibbsite, bayerite,boehmite, pseudoboehmite, and nordstrandite on one end of the spectrumand alpha alumina or corundum on the other. Such transition aluminas maybe viewed as metastable phases. A scheme of the transformation sequencecan be found in the text: Oxides and Hydroxides of Aluminum by K. Wefersand C. Misra; Alcoa Technical Paper No. 19, revised; copyright AluminumCompany of America Laboratories, 1987.

FCC catalyst compositions which include a zeolite component have acatalytically active crystallized aluminosilicate material, such as, forexample, a large-pore zeolite crystallized on or in a microspherecomprising non-zeolitic material. Large pore zeolite cracking catalystshave pore openings of greater than about 7 Angstroms in effectivediameter. Conventional large-pore molecular sieves include zeolite X;REX; zeolite Y; Ultrastable Y (USY); Rare Earth exchanged Y (REY); RareEarth exchanged USY (REUSY); Dealuminated Y (DeAl Y); Ultrahydrophobic Y(UHPY); and/or dealuminated silicon-enriched zeolites, e.g., LZ-210.According to one or more embodiments, the FCC catalyst comprisescatalytic microspheres comprising a crystalline aluminosilicate materialselected from zeolite Y, ZSM-20, ZSM-5, zeolite beta, zeolite L; andnaturally occurring zeolites such as faujasite, mordenite and the like,and a non-zeolitic component. These materials may be subjected toconventional treatments, such as calcinations and ion exchange with rareearths to increase stability.

Particles (e.g. microspheres) comprising hydrous kaolin clay and/ormetakaolin, a dispersible boehmite, optionally spinel and/or mullite,and a sodium silicate or silica sol binder can be prepared in accordancewith the techniques described in U.S. Pat. No. 6,716,338, which isincorporated herein by reference. For example, the catalysts can be madeby crystallizing the desired amount of sodium Y zeolite in porousmicrospheres composed of a mixture of two different forms of chemicallyreactive calcined clay, namely, metakaolin and spinel. The microspherescontaining the two forms of calcined kaolin clay are immersed in analkaline sodium silicate solution, which is heated, until the maximumobtainable amount of Y zeolite is crystallized in the microspheres. Theamount of zeolite according to embodiments of the invention is in therange of 20% to 95%, or 30% to 60%, or 30% to 45% by weight based on theweight of the FCC catalyst composition.

Preparation of Boron Oxide-Containing Particles

As described above, the FCC catalyst compositions can be providedutilizing first and second particle types. Alternatively, a FCC catalystcomposition can be provided wherein the boron can be incorporated into asingle particle type (an all-in-one particle—one or more boron oxidecomponents, nonzeolitic component, a zeolite component and optionallyone or more of a transition alumina component and a rare earthcomponent). In a FCC catalyst composition utilizing a single particletype, the boron can be incorporated in a variety of ways. In one or moreembodiments, the boron is placed on an all-in-one particle such that theboron is separated from the zeolite on the particle.

For example, boron oxide-containing particles can be prepared byimpregnating a matrix with boron. As used herein, the term “impregnated”means that a boron containing solution is put into pores of a material,such as a non-zeolitic component or a zeolite. In one or moreembodiments, particles are made utilizing the processes described inU.S. Pat. Nos. 5,559,067 and 6,716,338, as described further below inthe manufacture of the second particle type. Boron oxide can beincorporated during particle manufacture at various stages of theprocess. For example, boron oxide can be incorporated during particleformation such as during spray drying, after particle formation such asduring calcination or during ion exchange of the zeolite after theparticles are formed. One or more boron oxide components are present inan amount in the range of 0.005% and 7% by weight, including 0.005%,0.01%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.5%,2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5% and 7.0% byweight on an oxide basis based on the weight of the FCC catalystcomposition.

In one or more embodiments, one or more boron oxide components are mixedwith the FCC compatible inorganic particles and spray dried to form theparticles. In other embodiments, one or more boron oxide components arespray loaded onto FCC compatible inorganic particles. The loading canoccur by a variety of techniques such as impregnation, spray-coating,etc.

In still further embodiments, one or more boron oxide components areadded to FCC compatible inorganic particles during calcination of theparticles. The spray dried particles are formed in the usual way, andthe one or more boron oxide components can be added during calcination.

In an alternative embodiment, boron can be added to the zeolitecontaining particles during ion exchange, as described further below.

Preparation of Catalyst Compositions Including First and Second ParticleTypes

As mentioned above, catalyst compositions can be provided utilizing afirst particle type consisting essentially of one or more boron oxidesand matrix material and a second particle type containing matrixmaterial, zeolite, transition alumina, and a rare earth component. Afirst particle type containing boron oxide can be prepared by mixing amatrix component (e.g. metakaolin, spinel, kaolin, mullite, etc.) withboron oxide. In accordance with the methods described in U.S. Pat. Nos.5,559,067 and 6,716,338, which are incorporated herein by reference,microspheres comprising one or more boron oxide components, and a matrixcomponent including hydrous kaolin clay, gibbsite (alumina trihydrate),spinel, and a silica sol binder, for example, an aluminum stabilizedsilica sol binder, are prepared by spray drying. It will be understoodthat the first particle type does not incorporate a zeolite andtherefore, a subsequent zeolite crystallization step is not utilized tomake the first particle type. The microspheres are calcined to convertthe hydrous kaolin component to metakaolin. The spray dried microspherescan be washed before calcination to reduce the sodium content if the solbinder contains a water soluble source of sodium, converted to sodiumsulfate. One or more boron oxide components are then added and arepresent in an amount in the range of 0.005% and 7% by weight, including0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 0.005% and7% by weight, including 0.005%, 0.01%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%,0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%,5.0%, 5.5%, 6.0%, 6.5% and 7.0% by weight on an oxide basis based on theweight of the FCC catalyst composition.

Preparation of Second Particle Type

According to one or more embodiments, a second particle type is preparedby in situ techniques according to the processes established in U.S.Pat. No. 5,559,067 (the '067 patent) and U.S. Pat. No. 6,716,338 (the'338 patent), which are herein incorporated by reference in theirentireties. In general, the microspheres are first formed, and thezeolitic component is then crystallized in/on the microspheresthemselves to provide microspheres containing both zeolitic andnon-zeolitic components.

An aqueous slurry of finely divided hydrous kaolin, kaolin that has beencalcined through its characteristic exotherm, and binder is prepared.The slurry can optionally contain boehmite. In specific embodiments, thehydrous kaolin, calcined kaolin and binder are premixed in one tank andfed to the spray drier from one line. When present, an aqueous aluminaslurry, peptized such as with formic acid is introduced from a separateline immediately prior to when the whole mix enters the spray drier.Other mixing and injection protocols may also be useful. For example, apolymer dispersed alumina, for example dispersed with Flosperse® can beused in the process. The final slurry solids are about 30-70 wt. %. Theaqueous slurry is then spray dried to obtain microspheres comprising asilica bonded mixture of hydrated kaolin, kaolin that has been calcinedat least substantially through its characteristic exotherm (spinel, ormullite, or both spinel and mullite), and optionally boehmite.

The reactive kaolin of the slurry to form the microspheres can be formedof hydrated kaolin or calcined hydrous kaolin (metakaolin) or mixturesthereof as described in the '067 and '338 patents.

A commercial source of powdered kaolin calcined through the exotherm,may be used as the spinel component. Hydrated kaolin clay is convertedto this state by calcining the kaolin at least substantially completelythrough its characteristic exotherm under the conditions described inthe '338 patent. (The exotherm is detectable by conventionaldifferential thermal analysis, DTA.). After completion of calcination,the a calcined clay can be pulverized into finely divided particlesbefore being introduced into the slurry that is fed to a spray dryer.The spray dried product is repulverized. The surface area (BET) oftypical spinel form kaolin is low, e.g., 5-10 m²/g; however, when thismaterial is placed in a caustic environment such as that used forcrystallization, silica is leached, leaving an alumina-rich residuehaving a high surface area, e.g. 100-200 m²/g (BET).

Mullite can also be used as a matrix component. Mullite is made byfiring clay at temperatures above 2000° F. For example M93 mullite maybe made from the same kaolin clay, used for the preparation of spinelcomponent. Mullite can also be made from other kaolin clays. Mullite mayalso be made from Kyanite clay. Heating Kyanite clay to a hightemperature of 3000° F., provides a more crystalline, purer mullite inthe calcined product than that obtained from kaolin clay.

According to one or more embodiments, the alumina used to prepare themicrospheres is a highly dispersible boehmite. Dispersibility of thehydrated alumina is the property of the alumina to disperse effectivelyin an acidic media such as formic acid of pH less than about 3.5. Suchacid treatment is known as peptizing the alumina. High dispersion iswhen 90% or more of the alumina disperses into particles less than about1 micron. When this dispersed alumina solution is spray dried with thekaolin and binder, the resulting microsphere contains uniformlydistributed alumina throughout the microsphere.

After spray drying, the microspheres are washed and calcined at atemperature and for a time (e.g., for two to four hours in a mufflefurnace at a chamber temperature of about 1500° to 1550° F.) sufficientto convert the hydrated clay component of the micro spheres tometakaolin, leaving the spinel component of the microspheres essentiallyunchanged. In specific embodiments, the calcined microspheres compriseabout 30 to 70% by weight metakaolin, about 10 to 50% by weight spineland/or mullite and 0.5 to about 35% by weight transition phase alumina.In one or more embodiments, the transition phase alumina comprises oneor more of eta, chi, gamma, delta or theta phase. In specificembodiments, the surface area (BET, nitrogen) of the crystallineboehmite (as well as the transition alumina) is below 150 m²/g,specifically below 125 m²/g, and more specifically, below 100 m²/g, forexample, 30-80 m²/g.

In one or more embodiments, the catalyst comprises from about 1% to 35%,or 5% to 25%, or 10% to 20% by weight of a transition alumina component(e.g. boehmite).

When microspheres contain a zeolite, precursor microspheres, which aremicrospheres obtained by calcining a non-zeolitic matrix component and atransition alumina, are reacted with zeolite seeds and an alkalinesodium silicate solution, substantially as described in U.S. Pat. No.5,395,809, the teachings of which are incorporated herein bycross-reference. The microspheres are crystallized to a desired zeolitecontent (for example, 20-95% by weight, or 30-60% by weight, or 30-45%by weight), filtered, washed, ammonium exchanged, exchanged withrare-earth cations if required, calcined, exchanged a second time withammonium ions, and calcined a second time if required. The silicate forthe binder can be provided by sodium silicates with SiO₂ to Na₂O ratiosof from 1.5 to 3.5, more specifically, ratios of from 2.00 to 3.22.

In specific embodiments, the crystallized aluminosilicate materialcomprises from about 20 to about 95 wt. % zeolite Y, for example, 30% to60% by weight, or 30% to 45% by weight, expressed on the basis of theas-crystallized sodium faujasite form zeolite. In one or moreembodiments, the Y-zeolite component of the crystalline aluminosilicate,in their sodium form, have a crystalline unit cell size range of between24.64-24.73 Å, corresponding to a SiO₂/Al₂O₃ molar ratio of theY-zeolite of about 4.1-5.2.

After crystallization by reaction in a seeded sodium silicate solution,the microspheres contain crystalline Y-zeolite in the sodium form.Sodium cations in the microspheres are replaced with more desirablecations. This may be accomplished by contacting the microspheres withsolutions containing ammonium, yttrium cations, rare earth cations orcombinations thereof. In one or more embodiments, the ion exchange stepor steps are carried out so that the resulting catalyst contains lessthan about 0.7%, more specifically less than about 0.5% and even morespecifically less than about 0.4%, by weight Na₂O. After ion exchange,the microspheres are dried. Rare earth levels in the range of 0.1% to12% by weight, specifically 1-5% by weight, and more specifically 2-3%by weight are contemplated. More specifically, examples of rare earthcompounds are the oxides of lanthanum, cerium, praseodymium, andneodymium. Typically, the amount of rare earth added to the catalyst asa rare earth oxide will range from about 1 to 5%, typically 2-3 wt. %rare earth oxide (REO). In general, the temperature of the impregnatingsolution will range from about 70-200° F. at a pH of from about 2-5.

Subsequent to the rare earth exchange, the catalyst composition in theform of microspheres is dried and then calcined at a temperature of from800°-1200° F. The conditions of the calcination are such that the unitcell size of the zeolite crystals is not significantly reduced.Typically, the drying step, after rare earth exchange is to remove asubstantial portion of the water contained within the catalyst, andcalcination is conducted in the absence of added steam. The rare earthoxide-containing catalyst, subsequent to calcination, is now furtheracid exchanged, typically by ammonium ions to, again, reduce the sodiumcontent to less than about 0.5 wt. % Na₂O. The ammonium exchange can berepeated to ensure that the sodium content is reduced to less than 0.5wt. % Na₂O. Typically, the sodium content will be reduced to below 0.2wt. % as Na₂O.

The catalysts of the invention can also be used in conjunction withadditional V-traps. Thus, one or more embodiments, the catalyst furthercomprises a V-trap. The V-trap can be selected from one or moreconventional V-traps including, but not limited to, MgO/CaO. Withoutintending to be bound by theory, it is thought that MgO/CaO interactswith V₂O₅ through an acid/base reaction to give less harmful vanadates.

Another aspect of the present invention is directed to a method ofcracking a hydrocarbon feed under fluid catalytic cracking conditions.In one or more embodiments, the method comprises contacting thehydrocarbon feed with the boron oxide containing FCC catalystcomposition of one or more embodiments. In one or more embodiments, thehydrocarbon feed is a resid feed. In one or more embodiments, in a residfeed operation, one of Ni and V metals accumulate on the catalyst, andthe FCC catalyst composition is effective to reduce the detrimentaleffects nickel and vanadium during cracking, thus reducing coke andhydrogen yields.

Conditions useful in operating FCC units utilizing catalyst of theinvention are known in the art and are contemplated in using thecatalysts of the invention. These conditions are described in numerouspublications including Catal. Rev.-Sci. Eng., 18 (1), 1-150 (1978),which is herein incorporated by reference in its entirety. The catalystsof one or more embodiments are particularly useful in cracking residuumand resid-containing feeds.

A further aspect of the present invention is directed to a method ofmanufacturing a FCC catalyst composition. In one or more embodiments,the method comprises forming FCC compatible inorganic particlescontaining a non-zeolitic component and one or more boron oxides. Theone or more boron oxides can be impregnated onto the particles.Alternatively, the boron can be incorporated during spray drying, orusing other techniques such as coating, etc.

In one or more embodiments, the one or more boron oxides are mixed withthe non-zeolitic component and spray dried to form the particles. Inother embodiments, the one or more boron oxides are loaded ontonon-zeolitic particles. In still further embodiments, the one or moreboron oxides are added to non-zeolitic particles during calcination ofthe particles.

In some embodiments, the non-zeolitic material includes metakaolin,kaolin, mullite, spinel, and combinations thereof. The particle canfurther comprise a transition alumina, a rare earth component, and amolecular sieve or zeolite component intergrown in situ with theparticles, as described in U.S. Pat. Nos. 4,493,902 and 6,656,347. Inone or more embodiments, one or more boron oxides are added to theparticles including intergrown molecular sieve or zeolite during ionexchanges. According to one or more embodiments, the molecular sieve orzeolite and matrix can also be made using conventional techniques formixing molecular sieves and matrix materials. For example, zeolite ormolecular sieve components can be dry blended or wet ball milledtogether, and then added to a suitable matrix and further mixed. Thematrix and zeolite mixture can be extruded, pilled, dropped in an oilbath, etc. to form relatively large particles. For use in fluidized bedcatalytic cracking units the matrix-zeolite mixture can be spray dried,but any other means can be used to make fluidizable catalyst particles,such as crushing or grinding larger size extrudates or pills. Theinvention is now described with reference to the following examples.

EXAMPLES Example 1 Comparative

Calcined kaolin (mullite) slurry made to 49% solids was added to 59%solids hydrous kaolin, while mixing, using a Cowles mixer. The mixturewas screened and transferred to a spray dryer feed tank. The clay slurrywas spray dried with sodium silicate injected in-line just prior toentering the atomizer. Sodium silicate (3.22 modulus) was used at ametered ratio to target 5 weight percent as SiO₂. The target particlesize for the microspheres was 80 microns. The microspheres wereprocessed to grow 60-65% zeolite Y using an in situ crystallizationprocess. A sample of crystallized NaY microspheres (250 g) was ionexchanged to achieve a Na₂O of 2.0% using ammonium nitrate. Rare earth(lanthanum) was then added to 1 wt. % REO. The rare earth exchangedsample was calcined at 1000° F. for 2 hours to stabilize the catalystand facilitate zeolitic sodium removal. After calcinations, a series ofammonium nitrate ion exchanges was performed to <0.2 wt. % Na₂O.Finally, with the reduced sodium, a second calcination was done at 1100°F. for 2 hours in order to further stabilize the catalyst and reduceunit cell size. The catalyst composition is further impregnated with3000 ppm of nickel then aged in the presence of steam at between1350-1500° F. The catalytic activity and selectivity of the catalystcomposition is determined using Advanced Cracking Evaluation (ACE)reactors and protocols.

Example 2

A catalyst composition as described in Example 1 was prepared with boronoxide added until the catalyst contained 1.0 wt. % of a boron componenton an oxide basis.

Results

TABLE 1 Comparison of catalytic properties of catalyst formulations withand without boron oxide Catalytic Data at Constant Coke (8 wt %) Example# H₂ LPG Gasoline LCO HCO Conv. Cat/Oil Comp. 1.0 18.8 46.4 14.8 8.976.2 7.7 Example 1 Example 2 0.8 18.5 47.2 13.5 10.3 76.2 9.9

The results illustrate that when boron oxide is incorporated into theFCC catalyst composition, the result is lower hydrogen and highergasoline yields when processing hydrocarbons feeds, particularly residfeeds, contaminated with transition metals, such as nickel.

Comparative Example 3

Calcined kaolin (mullite) (36.6 kg) slurry made to 49% solids was addedto 59% solids hydrous kaolin (25.9 kg), while mixing, using a Cowlesmixer. Next a 56% solids boehmite alumina (14 kg) slurry was slowlyadded to the mixing clay slurry and was allowed to mix for more thanfive minutes. The mixture was screened and transferred to a spray dryerfeed tank. The clay/boehmite slurry was spray dried with sodium silicateinjected in-line just prior to entering the atomizer. Sodium silicate(20.2 kg, 3.22 modulus) was used at a metered ratio of 1.14 liter/minslurry:0.38 liter/min silicate. The target particle size for themicrospheres was 80 microns. Binder sodium was removed from the formedmicrospheres by slurrying the microspheres for thirty minutes andmaintaining the pH from 3.5-4 using sulfuric acid. Finally, the acidneutralized microspheres were dried and calcined at 1350-1500° F. fortwo hours. The microspheres were processed to grow 60-65% zeolite Yusing an in situ crystallization process. A sample of crystallized NaYmicrospheres (250 g) was ion exchanged to achieve a Na₂O of 2.0% usingammonium nitrate. Lanthanum was then added to 3 wt. % REO. The rareearth exchanged sample was calcined at 1000° F. for 2 hours to stabilizethe catalyst and facilitate zeolitic sodium removal. After calcinations,a series of ammonium nitrate ion exchanges was performed to achieve <0.2wt. % Na₂O. Finally, with the reduced sodium, a second calcination wasdone at 1100° F. for 2 hours in order to further stabilize the catalystand reduce unit cell size. The catalyst composition is furtherimpregnated with 3000 ppm each of nickel and vanadium and aged undercyclic reducing and oxidizing conditions in the presence of steam atbetween 1350-1500° F. The catalytic activity and selectivity of thecatalyst composition is determined using Advanced Cracking Evaluation(ACE) reactors and protocols.

Example 4

A catalyst composition as described in Example 1 was prepared. Particlescomprising matrix material and 7 wt. % boron oxide were prepared, andthese particles were mixed with the catalyst composition described inExample 1 in a ratio of 5% boron oxide particles and 95% of the catalystcomposition of Example 1 to provide a catalyst composition comprising0.35 wt. % of a boron component on an oxide basis.

ACE results at constant conversion (75 wt. %) of the four catalystexamples:

Comp. Example 3 Example 4 H2 0.81 0.59 Gasoline + LPG 57.86 61.55 LCO15.12 14.86 Coke 13.49 10.44 Activity at C/O = 7.7 3.57 3.76

Example 4 exhibited the lowest coke yield in the table above, andconsiderably lower H₂ yield compared to Comparative Example 3.

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference for allpurposes to the same extent as if each reference were individually andspecifically indicated to be incorporated by reference and were setforth in its entirety herein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the materials and methods discussed herein(especially in the context of the following claims) are to be construedto cover both the singular and the plural, unless otherwise indicatedherein or clearly contradicted by context. Recitation of ranges ofvalues herein are merely intended to serve as a shorthand method ofreferring individually to each separate value falling within the range,unless otherwise indicated herein, and each separate value isincorporated into the specification as if it were individually recitedherein. All methods described herein can be performed in any suitableorder unless otherwise indicated herein or otherwise clearlycontradicted by context. The use of any and all examples, or exemplarylanguage (e.g., “such as”) provided herein, is intended merely to betterilluminate the materials and methods and does not pose a limitation onthe scope unless otherwise claimed. No language in the specificationshould be construed as indicating any non-claimed element as essentialto the practice of the disclosed materials and methods.

Reference throughout this specification to “one embodiment,” “certainembodiments,” “one or more embodiments” or “an embodiment” means that aparticular feature, structure, material, or characteristic described inconnection with the embodiment is included in at least one embodiment ofthe invention. Thus, the appearances of the phrases such as “in one ormore embodiments,” “in certain embodiments,” “in one embodiment” or “inan embodiment” in various places throughout this specification are notnecessarily referring to the same embodiment of the invention.Furthermore, the particular features, structures, materials, orcharacteristics may be combined in any suitable manner in one or moreembodiments.

Although the invention herein has been described with reference toparticular embodiments, it is to be understood that these embodimentsare merely illustrative of the principles and applications of thepresent invention. It will be apparent to those skilled in the art thatvarious modifications and variations can be made to the method andapparatus of the present invention without departing from the spirit andscope of the invention. Thus, it is intended that the present inventioninclude modifications and variations that are within the scope of theappended claims and their equivalents.

What is claimed is:
 1. A fluid catalytic cracking (FCC) catalystcomposition for cracking hydrocarbons, the FCC catalyst compositioncomprising FCC compatible inorganic particles containing one or moreboron oxide components and cracking particles, the FCC catalystcomposition effective to reduce coke and hydrogen yields during crackingof metal-containing FCC feeds.
 2. The FCC catalyst composition of claim1, wherein the one or more boron oxide components are present in anamount in the range of 0.005% to 8% by weight of the composition.
 3. TheFCC catalyst composition of claim 2, wherein the cracking particlescomprise 20% to 95% by weight of a zeolite component.
 4. The FCCcatalyst composition of claim 3, wherein the FCC compatible inorganicparticle comprises a non-zeolitic component.
 5. The FCC catalystcomposition of claim 4, wherein the non-zeolitic component is selectedfrom the group consisting of kaolinite, halloysite, montmorillonite,bentonite, attapulgite, kaolin, amorphous kaolin, metakaolin, mullite,spinel, hydrous kaolin, clay, gibbsite (alumina trihydrate), boehmite,titania, alumina, silica, silica-alumina, silica-magnesia, magnesia andsepiolite.
 6. The FCC catalyst composition of claim 4, wherein thecracking particle contains oxide is selected from the group consistingof yttria, ceria, lanthana, praseodymia, neodymia, and combinationsthereof.
 7. The FCC catalyst composition of claim 6, wherein the rareearth component is lanthana, and the lanthana is present in a range of0.5 wt. % to about 5.0 wt. % on an oxide basis based on the weight ofthe FCC catalyst composition.
 8. The FCC catalyst composition of claim6, the cracking particle further comprising a transition aluminacomponent present in a range of 1 wt. % to 35 wt. %.
 9. The FCC catalystcomposition of claim 4, wherein the zeolite is intergrown with thenon-zeolitic component.
 10. The FCC catalyst composition of claim 4,wherein the zeolite component is mixed with the non-zeolitic component.11. The FCC catalyst composition of claim 1, wherein the one or moreboron oxide components are on the cracking particles.
 12. An FCCcatalyst composition for cracking hydrocarbons, the FCC catalystcomposition comprising a first particle type comprising one or moreboron oxide components and a first matrix component and a secondparticle type having a composition different from the first particletype, the second particle type comprising a second matrix component and20% to 95% by weight of a zeolite component, wherein the first particletype and second particle type are mixed together.
 13. The FCC catalystcomposition of claim 12, wherein the first and second matrix componentscomprise a non-zeolitic material.
 14. The FCC catalyst composition ofclaim 12, wherein the one or more boron oxide components are on secondparticle type.
 15. The FCC catalyst composition of claim 13, wherein thenon-zeolitic material is selected from the group consisting ofkaolinite, halloysite, montmorillonite, bentonite, attapulgite, kaolin,amorphous kaolin, metakaolin, mullite, spinel, hydrous kaolin, clay,gibbsite (alumina trihydrate), boehmite, titania, alumina, silica,silica-alumina, silica-magnesia, magnesia and sepiolite.
 16. A method ofcracking a hydrocarbon feed under fluid catalytic cracking conditions,the method comprising contacting the hydrocarbon feed with the FCCcatalyst composition of claim
 1. 17. A method of cracking a hydrocarbonfeed under fluid catalytic cracking conditions, the method comprisingcontacting the hydrocarbon feed with the FCC catalyst composition ofclaim
 12. 18. A method of manufacturing a fluid catalytic crackingcatalyst (FCC) composition, the method comprising forming particlescontaining a non-zeolitic component and one or more boron oxides. 19.The method of claim 18, wherein the one or more boron oxides areimpregnated onto the particles.
 20. The method of claim 18, wherein theone or more boron oxides are mixed with the non-zeolitic component andspray dried to form the particles.
 21. The method of claim 18, whereinthe formed particles further comprise a molecular sieve.
 22. The methodof claim 18, wherein the one or more boron oxides are loaded onnon-zeolitic particles.
 23. The method of claim 18, wherein one or moreboron oxide components are added to non-zeolitic particles duringcalcination of the particles.
 24. The method of claim 18, wherein thenon-zeolitic material is selected from the group consisting ofkaolinite, halloysite, montmorillonite, bentonite, attapulgite, kaolin,amorphous kaolin, metakaolin, mullite, spinel, hydrous kaolin, clay,gibbsite (alumina trihydrate), boehmite, titania, alumina, silica,silica-alumina, silica-magnesia, magnesia and sepiolite, the particlefurther comprising a transition alumina and a zeolite componentintergrown in situ with the particles.